Doping with multiple cations and failure of charge transfer in large ionized helium droplets.

We report experimental observations of aniline (A) cations and He2 + when aniline is doped into ionized helium droplets. Large droplets containing 108 atoms are bombarded by energetic electrons, resulting in more than one positive charge in one droplet. When aniline encounters the charged droplets, some are ionized via charge transfer, while others can remain neutral in the presence of He2 + when the mass-to-charge ratio (m/z) of the droplet is sufficiently large. Upon resonant excitation of the dopant An or An + (n ≥ 1), He2 + can be ejected. The excitation spectrum of He2 + becomes a juxtaposition of the spectra of An and An +. Moreover, an anticorrelation between the yields of He2 + and A+ is observed with increasing energies of the ionizing electrons. We attribute this result to the combined effect of reduction in m/z of the droplets and the different locations of He2 + and neutral An. Limited by the penetration depths of the ionizing electrons and further assisted by the Coulomb repulsion of coexisting cations, He2 + is located within 20 nm of the surface, while neutral An has an average position inside a large droplet. Upon resonant excitation of the interior An, He2 + is preferentially ejected. With increasing energies of the colliding electrons, the m/z of the droplets are reduced, leading to less effective charge shielding and more effective charge transfer, until ultimately, all He2 + can be neutralized to form A+.